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The extent of oxidation of hydrocarbons desorbing from the oil layer has been measured directly in a hydrogen-fueled, spark-ignited engine in which the lubricant oil was doped with a single component hydrocarbon. The amount of hydrocarbon desorbed and oxidized could be measured simultaneously as the dopant was only source of carbon-containing species. The fraction oxidized was strongly dependent on engine load, hydrogen fuel-air ratio and dopant chemical reactivity, but only modestly dependent on spark timing and nitrogen dilution levels below 20 percent. Fast FID measurements at the cylinder exit showed that the surviving hydrocarbons emerge late in the exhaust stroke.

The engine-out (EO) total and speciated hydrocarbon emissions data from the Auto-Oil Program Phase II Heavy Hydrocarbon Study had been analyzed. The methodology was to first investigate the stabilized EO emissions (Bag 2) of a specific vehicle (Vehicle 04B, a 1989 Model Year Ford Taurus); then the vehicle-to-vehicle differences in Bag2 emissions were considered. Finally, the differences in the Bag2 and the starting/warm-up EO emissions (Bag1) were examined. The speciated emissions may be interpreted as a “feed-through” part due to the unreacted fuel species, and an “offset” part due to the decomposition products. The significant non-fuel emitted species were methane and the olefins. The HC emissions for vehicles with different total emissions were similar in species composition. For both the total and speciated emissions, there was no substantial difference between the Bag1 and Bag2 values for Vehicle 04B.

A technique has been developed to measure the desorption and subsequent oxidation of fuel in the oil layer by spiking the oil with liquid fuel and firing the engine on gaseous fuel or motoring with air. Experiments suggest that fuel desorption is not diffusion limited above 50 °C and indicated that approximately two to four percent of the cylinder oil layer is fresh oil from the sump. The increase in hydrocarbon emissions is of the order of 100 ppmC1 per 1% liquid fuel introduced into the fresh oil in a methane fired engine at mid-speed and light load conditions. Calculations indicate that fuel desorbing from oil is much more likely to produce hydrocarbon emissions than fuel emerging from crevices.

The chemistry of unburned hydrocarbon oxidation in SI engine exhaust was modeled as a function of temperature and concentration of unburned gas for lean and rich mixtures. Detailed chemical kinetic mechanisms were used to model isothermal reactions of unburned fuel/air mixture in an environment of burned gases at atmospheric pressure. Simulations were performed using five pure fuels (methane, ethane, propane, n-butane and toluene) for which chemical kinetic mechanisms and steady state hydrocarbon (HC) emissions data were available. A correlation is seen between reaction rates and HC emissions for different fuels. Calculated relative amounts of intermediate oxidation products are shown to be consistent with experimental measurements.

The autoignition characteristics of methanol, ethanol and MTBE (methyl tert-butyl ether) have been investigated in a rapid compression machine at pressures in the range 20-40 atm and temperatures within 750-1000 K. All three oxygenated fuels tested show higher autoignition temperatures than paraffins, a trend consistent with the high octane number of these fuels. The autoignition delay time for methanol was slightly lower than predicted values using reported reaction mechanisms. However, the experimental and measured values for the activation energy are in very good agreement around 44 kcal/mol. The measured activation energy for ethanol autoignition is in good agreement with previous shock tube results (31 kcal/mol), although ignition times predicted by the shock tube correlation are a factor of three lower than the measured values. The measured activation energy for MTBE, 41.4 kcal/mol, was significantly higher than the value previously observed in shock tubes (28.1 kcal/mol).

The combustion behavior in a modem 4-valve engine using a broad range of methanol/gasoline fuel mixtures was studied. The initial flame development was examined by using a spark plug fiber optics probe. Approximately, the kernel expansion speed, Sg, is relatively unchanged from M0 to M40; jumps by ∼30% from M40 to M60; and then remains roughly constant from M60 to M100. Statistics of the IMEP indicate that at a lean idle condition the combustion rate and robustness correlate with Sg: a higher value of Sg gives better combustion. Thus M60-M100 fuels give better idle combustion behavior than the M0-M40 fuels.

Natural gas powered vehicles are attractive in certain applications due to their lower emissions in general than conventional diesel engines and the low cost of natural gas. For stoichiometric natural gas engines, the aftertreatment system typically consists only of a three-way catalyst (TWC). However, increasingly stringent NOx and methane regulations challenge current TWC technologies. In this work, a catalyst reactor system with variable lean/rich switching capability was developed for evaluating TWCs for stoichiometric natural gas engines. The effect of varying frequency and duty-cycle during lean/rich gas switching experiments was measured with a hot-wire anemometer (HWA) due to its high sensitivity to gas thermal properties. A theoretical reactor gas dispersion model was then developed and validated with the HWA measurements. The model is capable of predicting the actual lean/rich gas exposure to the TWC under different testing conditions.

Long-haul and other heavy-duty trucks, presently almost entirely powered by diesel fuel, face challenges meeting worldwide needs for greatly reducing nitrogen oxide (NOx) emissions. Dual-fuel gasoline-alcohol engines could potentially provide a means to cost-effectively meet this need at large scale in the relatively near term. They could also provide reductions in greenhouse gas emissions. These spark ignition (SI) flexible fuel engines can provide operation over a wide fuel range from mainly gasoline use to 100% alcohol use. The alcohol can be ethanol or methanol. Use of stoichiometric operation and a three-way catalytic converter can reduce NOx by around 90% relative to emissions from diesel engines with state of the art exhaust treatment.

Higher compression ratio and turbocharging, with engine downsizing can enable significant gains in fuel economy but require engine operating conditions that cause engine knock under high load. Engine knock can be avoided by supplying higher-octane fuel under such high load conditions. This study builds on previous MIT papers investigating Octane-On-Demand (OOD) to enable a higher efficiency, higher-boost higher compression-ratio engine. The high-octane fuel for OOD can be obtained through On-Board-Separation (OBS) of alcohol blended gasoline. Fuel from the primary fuel tank filled with commercially available gasoline that contains 10% by volume ethanol (E10) is separated by an organic membrane pervaporation process that produces a 30 to 90% ethanol fuel blend for use when high octane is needed. In addition to previous work, this paper combines modeling of the OBS system with passenger car and medium-duty truck fuel consumption and octane requirements for various driving cycles.

Non-petroleum based liquid fuels are essential for reducing oil dependence and greenhouse gas generation. Increased substitution of alcohol fuel for petroleum based fuels could be achieved by 1) use in high efficiency spark ignition engines that are employed for heavy duty as well as light duty operation and 2) use of methanol as well as ethanol. Methanol is the liquid fuel that is most efficiently produced from thermo-chemical gasification of coal, natural gas, waste or biomass. Ethanol can also be produced by this process but at lower efficiency and higher cost. Coal derived methanol is in limited initial use as a transportation fuel in China. Methanol could potentially be produced from natural gas at an economically competitive fuel costs, and with essentially the same greenhouse gas impact as gasoline. Waste derived methanol could also be an affordable low carbon fuel.

Ethanol and acetaldehyde emissions from a direct ignition spark ignition were measured using mass spectrometry. Previous methods focused on eliminating or minimizing interference from exhaust species with identical atomic mass and fragment ions created in ionization process. This paper describes a new technique which exploits the fragment ions from ethanol and acetaldehyde. A survey of mass spectra of all major species of exhaust gas was conducted. It was found that ethanol contributes most ions in mass number 31 and that no other gas species produces ions at this mass number. Acetaldehyde detection suffers more interference. Nevertheless, it was estimated that detection at mass number 43 is possible with 10% error from 2-methylbutane. This new technique was validated in an engine experiment. By running the engine with pure gasoline and E85, the validity of the technique can be checked.

The use of hydrogen as a fuel supplement for lean-burn engines at higher compression ratios has been studied extensively in recent years, with good promise of performance and efficiency gains. With the advances in reformer technology, the use of a gaseous fuel stock, comprising of substantially higher fractions of hydrogen and other flammable reformate species, could provide additional improvements. This paper presents the performance and emission characteristics of a gas mixture of equal volumes of hydrogen, CO, and methane. It has recently been reported that this gas mixture can be produced by reforming of ethanol at comparatively low temperature, around 300C. Experiments were performed on a 1.8-liter passenger-car Nissan engine modified for single-cylinder operation. Special pistons were made so that compression ratios ranging from CR= 9.5 to 17 could be used. The lean limit was extended beyond twice stoichiometric (up to lambda=2.2).

The fuel effects on HCCI operation in a spark assisted direct injection gasoline engine are assessed. The low load limit has been extended with a pilot fuel injection during the negative valve overlap (NVO) period. The fuel matrix consists of hydrocarbon fuels and various ethanol blends and a butanol blend, plus fuels with added ignition improvers. The hydrocarbon fuels and the butanol blend do not significantly alter the high or the low limits of operation. The HCCI operation appears to be controlled more by the thermal environment than by the fuel properties. For E85, the engine behavior depends on the extent that the heat release from the pilot injected fuel in the NVO period compensates for the evaporative cooling of the fuel.

Regulations on methane emissions from lean-burn natural gas (NG) and lean-burn dual fuel (natural gas and diesel) engines are becoming more stringent due to methane’s strong greenhouse effect. Palladium-based oxidation catalysts are typically used for methane reduction due to their relative high reactivity under lean conditions. However, the catalytic activity of these catalysts is inhibited by the water vapor in exhaust and decreases over time from exposure to trace amounts of sulfur. The reduction of deactivated catalysts in a net rich environment is known to be able to regenerate the catalyst. In this work, a multicycle methane light-off & extinction test protocol was first developed to probe the catalyst reactivity and stability under simulated exhaust conditions. Then, the effect of two different regeneration gas compositions, denoted as regen-A and regen-B, was evaluated on a degreened catalyst and a catalyst previously tested on a natural gas engine.

A one-dimensional model has been developed for the species and energy transfer over a thin (0.1-0.5 mm) layer of liquid fuel present on the wall of a spark-ignition engine. Time-varying boundary conditions during compression and flame passage were used to determine the rate of methanol vaporization and oxidation over a mid-speed, mid-load cycle, as a function of wall temperature. The heat of vaporization and the boiling point of the fuel were varied about a baseline to determine the effect of these characteristics, at a fixed operating point and lean conditions (ϕ = 0.9). The calculations show that the evaporation of fuels from layers on cold walls starts during flame passage, peaking a few milliseconds later, and continuing through the exhaust phase.

Hydrogen can be readily used in spark-ignition engines as a clean alternative to fossil fuels. However, a larger burning velocity and a shorter quenching distance for hydrogen as compared with hydrocarbons bring a larger cooling loss from burning gas to the combustion-chamber wall. Because of the large cooling loss, the thermal efficiency of a hydrogen-fueled engine is sometimes lower than that of a conventionally fueled engine. Therefore, the reduction of the cooling loss is very important for improving the thermal efficiency in hydrogen-combustion engines. On the other hand, the direct-injection stratified charge can suppress knocking in spark-ignition engines at near stoichiometric overall mixture conditions. Because this is attributed to a leaner end gas, the stratification can lead to a lowered temperature of burning gas around the wall and a reduced cooling loss.

The transportation sector in the United States is a major contributor to global energy consumption and carbon dioxide emission. To assess the future potentials of different technologies in addressing these two issues, we used a family of simulation programs to predict fuel consumption for passenger cars in 2020. The selected technology combinations that have good market potential and could be in mass production include: advanced gasoline and diesel internal combustion engine vehicles with automatically-shifting clutched transmissions, gasoline, diesel, and compressed natural gas hybrid electric vehicles with continuously variable transmissions, direct hydrogen, gasoline and methanol reformer fuel cell hybrid electric vehicles with direct ratio drive, and battery electric vehicle with direct ratio drive.

The spark ignition engine particulate number (PN) emissions have been correlated to a particulate matter index (PMI) in the literature. The PMI value addresses the fuel effect on PN emission through the individual fuel species reactivity and vapor pressure. The latter quantity is used to account for the propensity of the non-volatile fuel components to survive to the later part of the combustion event as wall liquid films, which serve as sources for particulate emission. The PMI, however, does not encompass the suppression of vaporization by the evaporative cooling of fuel components, such as ethanol, that have high latent heat of vaporization. This paper assesses this evaporative cooling effect on PN emissions by measurements in a GDI engine operating with a base gasoline which does not contain oxygenate, with a blend of the gasoline and ethanol, and with a blend of the gasoline, ethanol, and a hydrocarbon additive so that the blend has the same PMI as the original gasoline.

The engine out particular matter number (PN) distributions at engine coolant temperature (ECT) of 0° C to 40° C for ethanol/ gasoline blends (E0 to E85) have been measured for a direct-injection spark ignition engine under cold fast idle condition. For E10 to E85, PN increases modestly when the ECT is lowered. The distributions, however, are insensitive to the ethanol content of the fuel. The PN for E0 is substantially higher than the gasohol fuels at ECT below 20° C. The total PN values (obtained from integrating the PN distribution from 15 to 350 run) are approximately the same for all fuels (E0 to E85) when ECT is above 20° C. When ECT is decreased below 20° C, the total PN values for E10 to E85 increase modestly, and they are insensitive to the ethanol content. For E0, however, the total PN increases substantially. This sharp change in PN from E0 to E10 is confirmed by running the tests with E2.5 and E5. The midpoint of the transition occurs at approximately E5.

The oxidation of short-chain alkanes, such as methane, ethane, and propane, from the exhaust of lean-burn natural gas and lean-burn dual-fuel (natural gas and diesel) engines poses a unique challenge to the exhaust aftertreatment community. Emissions of these species are currently regulated by the US Environmental Protection Agency (EPA) as either methane (Greenhouse Gas Emissions Standards) or non-methane hydrocarbon (NMHC). However, the complete catalytic oxidation of short-chain alkanes is challenging due to their thermodynamic stability. The present study focuses on the oxidation of short-chain alkanes by vanadium-based and Cu/zeolite selective catalytic reduction (SCR) catalysts, generally utilized to control NOx emissions from lean-burn engines. Results reveal that these catalysts are active for short-chain alkane oxidation, albeit, at conversions lower than those generally reported in the literature for Pd-based catalysts, typically used for short-chain alkane conversion.